KR20220119416A - Two part curable composition - Google Patents

Abstract

A two part curable composition is provided comprising a first part comprising a (meth)acrylate component and an amine and a second part comprising a fatty acid peroxide. A method of making a two-part adhesive composition using the two-part curable composition and a method of bonding a surface using the two-part curable composition are further disclosed.

Description

Two part curable composition

The present invention provides a two part curable composition comprising a first part comprising a (meth)acrylate component and an amine and a second part comprising a fatty acid peroxide.

Acrylic adhesive compositions are well known. See, eg, US Pat. No. 4,536,546 (Briggs). Adhesives based on this technology appear to be sold under the trade names PLEXUS MA 300 and 310 by Illinois Tool Works Inc. (Chicago, Illinois, USA). These adhesives can exhibit a disgusting odor and they are toxic to handle, which can be recognized as a significant disadvantage in their use.

US Patent Application Publication No. 2010/0065210 discloses (a) (i) a (meth)acrylic component, (ii) an amine catalyst; (iii) an optional second catalyst; (iv) a first moiety comprising a reactive acid component, and (v) a free-radical inhibitor; and (b) (i) a resin component comprising an epoxy group, (ii) a peroxide; and (iii) a second portion comprising a metal compound complexed with the strong acid component and substantially non-reactive with the peroxide. The first and second portions have sufficiently low viscosities for easy dispensing into the pumping device. To form this adhesive, the first and second parts are mixed, and immediately after mixing, the mixture has a higher viscosity, so that after application to the surface within the open time of the mixture, the adhesive sags, drips, Without moving, the mixed first and second parts are cured. The term "open time" means the elapsed time until the mixture of adhesives is cured.

U.S. Patent No. 9,574,118 (Cheng)

(a) (i) a (meth)acrylic component at least a portion of which comprises isobornyl (meth)acrylate;

(ii) an amine catalyst;

(iii) vinyl terminated polybutadiene in liquid form at room temperature;

(iv) a reactive acid component;

(v) solid zinc (meth)acrylate salts;

(vi) zinc and/or bismuth complexes; and

(vii) free-radical inhibitors

a first part comprising; and

(b) (i) a resin component comprising an epoxy group;

(ii) benzoyl peroxide;

(iii) plasticizers; and

(iv) optionally, a block copolymer

a second part comprising

wherein the first and second portions are mixed and applied to at least one substrate.

U.S. Patent No. 8,921,490 (Levandoski)

a. i. at least one (meth)acrylate monomer;

ii. a first halogen-free elastomer comprising a styrene-butadiene-styrene block copolymer;

iii. acid catalyst;

iv. free radical initiators; and

v. free radical stabilizer

a first part comprising; and

b. i. at least one (meth)acrylate monomer;

ii. a second halogen-free elastomer;

iii. catalyst; and

iv. Stabilizer for stabilizing the catalyst

a second part comprising

wherein the first part and the second part are combined together to form the curable composition.

U.S. Patent No. 6,433,091 (Cheng) relates to a (meth)acrylate ester-containing two-part reactive adhesive composition comprising a vinyl-terminated liquid rubber and a polymeric elastomer. The vinyl-terminated liquid rubber is preferably (meth)acrylate-terminated polybutadiene; The polymer elastomer is preferably polychloroprene, a core shell polymer and/or a block copolymer rubber.

U.S. Patent No. 6,291,593 (Cheng) consists essentially of 10-90 weight percent ester monomer, about 2-85 weight percent polymeric elastomer, about 0.02-10 weight percent initiator, and about 0.005-7 weight percent retardation additive, wherein the retardation additive is selected from the group consisting of aprotic Lewis acids and zinc salts and mixtures thereof, and the ester monomer is selected from the group consisting of methacrylate ester monomers, acrylate ester monomers and mixtures thereof, wherein the retardation and the additive is present in an amount effective to (a) extend the open time of the adhesive composition by at least 5 minutes or (b) reduce the peak exothermic temperature of the adhesive composition by at least 15°F.

U.S. Patent No. 9,657,203 (Murray) is

(a) (i) a (meth)acrylate component;

(ii) 1,4-quinones such as naphthoquinone or benzoquinone and derivatives thereof in an amount of up to about 0.05 weight percent;

(iii) triaryl or alkaryl phenylphosphine in an amount of at least about 0.5 weight percent; and

(iv) amines

A first part comprising; and

(b) (i) benzoyl peroxide in an amount greater than about 1.0 weight percent

a second part comprising

It relates to a two-part curable composition comprising a.

The composition of the '203 patent is less than about 80 seconds at a bondline temperature of 40°C when used to adhesively bond substrates such as different ones, one constructed from plastic-like PC/ABS and the other constructed from metal-like anodized aluminum. has been reported to have a fixation time of The composition of the '203 patent is reported to have a shelf life at a temperature of 38° C. of greater than 4 weeks.

In addition, International Patent Publication No. WO 2017/172270 (Messana) is

Part A: at least one compound in structure I :

(wherein A is CH ₂ or benzyl, R is C _1-10 alkyl, R′ is H or C _1-10 alkyl, or R and R′ together form a 4-7 membered ring fused to a benzyl ring and R" is optional, but when R" is present, R" is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene- ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl or haloalkyl, where EWG is an electron withdrawing group; and

Part B: Oxidizer

wherein at least one of Part A or Part B comprises a (meth)acrylate component.

Despite the state of the art, existing compositions do not have the desired combination of long open time characteristics and sharp cure characteristics desired for many assembly applications. Accordingly, a need exists for such compositions.

That need remains unmet to date.

summary

On one side,

(a) (i) a (meth)acrylate component; and

(ii) amines

Part A composition comprising; and

(b) (i) fatty acid peroxide

Part B composition comprising

A two-part curable composition comprising:

When the Part A composition and the Part B composition are mixed together at room temperature (ie, room temperature is about 25° C.), the mixed composition, as measured by a PICO Technologies USB TC-08 thermocouple data logger, is at least about It exhibits an open time of 3 hours but then reaches its peak cure temperature (or T _peak ) in less than about 1 hour.

In another aspect, the present invention provides a method for improving the open time of a two part curable composition and sharpening the time difference between the temperature at which the onset of cure begins and the peak cure temperature is reached.

1 shows a plot of curing temperature over time captured by a Pico Technologies USB TC-08 thermocouple data logger.

details

As mentioned above, the composition of the present invention comprises a Part A composition comprising a (meth)acrylate component and an amine and a Part B composition comprising a fatty acid peroxide.

When the Part A composition and the Part B composition are mixed together at room temperature (ie, the room temperature is about 25° C.), the mixed composition has an open time of at least about 3 hours, as measured by a Pico Technologies USB TC-08 thermocouple data logger. time, but reach its peak cure temperature (or T _peak ) within about an hour after that.

Part A

(meth)acrylate component

Any suitable material containing at least one group having the formula:

wherein R is selected from H or C ₁ alkyl.

Advantageously, the group is a (meth)acrylate or (meth)acryloxy group, which is intended to refer to both acrylate and methacrylate, wherein R is H or methyl respectively. Useful amounts of the (meth)acrylate component typically range from about 20 weight percent to about 80 weight percent of the total composition. Preferably, the composition of the present invention contains from about 50 weight percent to about 70 weight percent of the (meth)acrylate component. In some embodiments, at least a portion of the (meth)acrylate component is isobornyl (meth)acrylate. For example, from about 5 weight percent to about 35 weight percent of the composition of the present invention should be isobornyl (meth)acrylate.

The (meth)acrylate component may be present in the form of a polymer, a monomer, or a combination thereof. When present in the form of a polymer, the (meth)acrylate component may be a polymer chain to which at least one of a (meth)acrylate or (meth)acryloxy group is attached. The groups may be located at pendant or terminal positions of the backbone, or a combination thereof.

Advantageously, at least two such groups may be present and may be located in terminal positions. The (meth)acrylate component, as is well known to those of ordinary skill in the art, is a polyvinyl, polyether, polyester, polyurethane, polyamide, epoxy, vinyl ester, phenol, amino resin, oil base, etc. polymer chains constructed from, or random or block combinations thereof.

Polymer chains can be formed by polymerization of vinyl monomers. Illustrative examples of such vinyl monomers are methyl (meth)acrylate, (meth)acrylic acid, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl ( Meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrime Toxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate , 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth) ) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylol propane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, Ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butylene glycol diacrylate, trime Thilopropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, tri( Propylene glycol) di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate ) acrylates, butylene glycol di(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate. Each of these monomers may be used alone or a plurality of them may be copolymerized.

Particularly preferred are {meth)acrylate ester monomers, including those in which the alcohol portion of the ester group contains C _1-8 . For example, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 1,3-butanediol dimethacrylate (“BDMA”), butyl methacrylate and Methyl methacrylate (“MMA”) is an example.

The (meth)acrylate component may be included in about 10 to about 90 weight percent of the composition, such as about 60 to 90 weight percent, based on the total weight of the composition.

amine

The composition of the present invention comprises at least one amine. The amine(s) acts as a catalyst by accelerating or otherwise accelerating the curing of the compositions of the present invention. The amine is preferably a sterically hindered secondary amine or a tertiary amine. Suitable amines are, for example, selected from the formula N-RR ₂ R ₃ , wherein R is hydrogen (for secondary amines) or alkyl (and hydroxy substituted versions thereof), aryl, alkaryl or aralkyl radicals and C _1-10 alkyl, C _6-18 aryl, C _7-15 alkaryl, and C _7-15 aralkyl radicals). The R ₂ and R ₃ groups may be linked such that the nitrogen is embedded within the cyclic structure, which itself may be fused to an aromatic ring system. Otherwise, R ₂ and R ₃ may each independently be R.

Particularly useful amines for inclusion in Part A of the compositions of the present invention include those in Structure A :

wherein R is optional but, if present, may occur 1-4 times, interrupted by one or more heteroatoms and/or C which may be functionalized by halogen, -OH, -COOH, -CN, -NH ₂ or -NO ₂ . _1-5 alkyl; halogen; -OH; -COOH; -CN; -NH ₂ or -NO ₂ ; X is C _1-5 alkyl or C _7-20 alkaryl, one of which may be interrupted by one or more heteroatoms, which are functionalized by at least one electron withdrawing group, —CN or —NO ₂ ; z is 1-3.

For example, an amine in structure A may be selected wherein X is C ₁ alkyl or C ₇ alkaryl substituted on the aromatic ring by at least one electron withdrawing group. Examples of such amines include:

Compounds in structure A can be prepared from

The amine should be present in an amount from about 0.01 weight percent to about 5 weight percent. Preferably, the amine is present in an amount from about 0.05 weight percent to about 2 weight percent. More preferably, the amine should be present in an amount from about 0.3 weight percent to about 0.7 weight percent.

Vinyl-Terminated Polybutadiene

If present, the vinyl-terminated polybutadiene should be in liquid form at room temperature. The vinyl-terminated polybutadiene should have a glass transition temperature of less than 0°C. Vinyl-terminated is (meth)acrylate-terminated, for example (meth)acrylate-terminated polybutadiene-acrylonitrile copolymers such as HYCAR VTBN, or (meth)acrylate-terminated polybutadiene such as HYCAR VTB (each from BF Goodrich). The vinyl-terminated polybutadiene should be present in an amount up to about 20 weight percent, such as from about 5 weight percent to about 15 weight percent.

reactive acid component

The composition of the present invention may include an acid or acid ester such as phosphoric acid or a derivative thereof, a phosphate acid ester, and a sulfonic acid or a derivative thereof as the reactive acid component. A preferred reactive acid component is a phosphate acid ester.

The acid may be selected from free-radically polymerizable acids such as ethylenically unsaturated mono or polycarboxylic acids, maleic acid and crotonic acid. Preferred include methacrylic acid (“MAA”) and acrylic acid.

The reactive acid component also controls and slows the curing time of the composition.

Suitable phosphate esters include those represented by the formula:

wherein R ¹ is H or CH ₃ and R ² is H or a radical represented by the structure:

wherein R ¹ is H or CH ₃ . A particularly useful phosphate ester is the hydroxyl ethyl methacrylate phosphate ester, sold under the trade designations T-MULZ 1228 or HARCRYL 1228 or 1228M, available from Harcros Chemicals, Kansas City, Kansas, respectively. Also, structures having at least one strong acid “active hydrogen” group, or having at least one phosphonic acid active hydrogen group (R ₁ R ₂ POOH), such as hydroxyl ethyl diphosphonic acid, phosphonic acid, and derivatives, or phosphonic acid Also included are oligomeric or polymeric structures having functional groups or similar acid strength functional groups.

When present, the reactive acid component is present from about 0.25 weight percent to about 15 weight percent of the composition. Preferably, when the reactive acid component is a phosphate ester, it is present in from about 1.0 to about 4.0 weight percent of the composition.

1,4-quinone

When present, certain 1,4-quinones may be used to stabilize the compositions of the present invention.

One such 1,4-quinone is naphthoquinone; Others are anthroquinones and benzoquinones.

Naphthoquinone may be used in the first portion of the composition in an amount up to about 0.005 weight percent.

Preferably, the amount is about 0.004 weight percent or less, such as about 0.0035 weight percent or less.

Aryl phosphine

When present, an aryl phosphine may be used in the first Part A composition. Aryl phosphine is tri(o-tolyl)phosphine, tris(4-methoxyphenyl)phosphine, diphenyl(p-tolyl)phosphine, diphenyl(o-tolyl)phosphine, tris(o-methoxy phenyl)phosphine, tri(p-tolyl)phosphine, diphenyl(2-methoxyphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, and of course triphenylphosphine.

Triphenylphosphine is used in an amount of at least about 0.5 weight percent, such as at least about 0.75 weight percent.

other additives

The Part A composition may also contain additional additives such as fillers, core shell polymers, lubricants, thickeners, and colorants. The filler provides bulk without sacrificing the strength of the adhesive and can be selected from high or low density fillers. In addition, certain fillers, such as silica, may impart rheological modification or small particle reinforcement. Commercially available examples include Cab-O-Sil 610 and AEROSIL R8200.

Low-density fillers are of particular importance because the resulting final product would otherwise have a lower density than a filler-free product, but would have the same strength characteristics as without fillers.

The core shell polymer is preferably a "core shell" type graft copolymer, or also "shell-free" crosslinked rubbery microparticles such as acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS) ), and methacrylate-acrylonitrile-butadiene-styrene (MABS). BLENDEX 338 is an ABS powder from GE Plastics.

Part B

fatty acid peroxide

Instead of the presently conventional benzoyl peroxide, a peroxide such as a fatty acid peroxide, such as lauroyl peroxide, is a preferred choice for use in the second part. In addition to lauroyl peroxide having a straight-chain C ₁₁ alkyl group attached to the carbonyl carbon of the carboxylic acid forming the peroxide, other fatty acid peroxides may be used. For example, fatty acid peroxides having a chain length of 8 to 18 carbon atoms may be used. Of particular interest are those having 9, 11, 14 and 16 carbon atoms attached to the carbonyl carbon of the carboxylic acid forming the peroxide.

Lauroyl peroxide is shown below:

A commercially available example of lauroyl peroxide is sold under the trade name LUPEROX LP from Arkema, Inc.

Fatty acid peroxides having straight chains of C ₉ , C ₁₄ and C ₁₆ are shown below as didecanoyl peroxide, dimyristyl peroxydicarbonate and dicetyl peroxydicarbonate, respectively, and these are Akzo Nobel NV (Akzo Nobel NV) is commercially available as a member of the PERKADOX trade name product line.

The fatty acid peroxide should be present in an amount from about 20 weight percent to about 60 weight percent of the Part B composition. Preferably, the fatty acid peroxide is present in an amount from about 25 weight percent to about 50 weight percent. More preferably, the fatty acid peroxide should be present in an amount from about 35 weight percent to about 45 weight percent.

epoxy resin

Epoxy resins are optional components, but if present, cycloaliphatic epoxides, epoxy novolac resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, bisphenol-A epichlorohydrin-based epoxy resins, alkyl epoxides, limonene dioxide , and polyepoxides.

A preferred resin component is a cycloaliphatic epoxide sold under the trade name CYRACURE UVR-6110 by Dow Chemical.

Another suitable resin component is a bisphenol-based liquid epoxy resin, such as those sold under the trade designation "D.E.R." by Dow Chemical. "D.E.R." suitable in the present invention Examples of products are D.E.R. 332 (diglycidyl ether of bisphenol-A); D.E.R. 330 (low viscosity, non-diluted, bisphenol-A liquid epoxy resin); D.E.R. 383 (low viscosity, non-diluted, bisphenol-A liquid epoxy resin); D.E.R. 354 (standard, bisphenol-F-based liquid epoxy resin); D.E.R. 351 (low viscosity, liquid bisphenol-A/F resin blend); D.E.R. 352 (low viscosity, liquid bisphenol-A/F resin blend); D.E.R. 324 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); D.E.R. 323 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); D.E.R. 325 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); and D.E.R. 353 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin). A different trade name for a bisphenol-based liquid epoxy resin suitable for use herein is EPON 828, which is derived from bisphenol A and epichlorohydrin and is commercially available from Hexion Specialty Chemicals.

Another suitable resin component is an epoxy novolac resin, which is a product of epichlorohydrin and phenol-formaldehyde novolac, sold under the trade name D.E.N. by Dow Chemical. "D.E.N." suitable for the present invention Examples of products are D.E.N. 431 (low viscosity semi-solid epoxy novolac resin); and D.E.N. 438 (semi-solid epoxy novolac resin).

Other suitable epoxy resins include polyepoxides curable with a catalyst or curing agent at ambient temperature or at a suitable elevated temperature. Examples of these polyepoxides are the reaction of suitable epichlorohydrin with a compound containing at least two free alcoholic hydroxyl and/or phenolic hydroxyl groups per molecule under alkaline conditions or, alternatively, in the presence of an acidic catalyst. and polyglycidyl and poly(β-methylglycidyl) ether obtainable by subsequent treatment with alkali. These ethers include acyclic alcohols such as ethylene glycol, diethylene glycol, and higher poly(oxyethylene) glycol, propane-1,2-diol and poly(oxypropylene) glycol, propane-1,3-diol, butane. -1,4-diol, poly(oxytetramethylene) glycol, pentane-1,5-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, from sorbitol, and poly(epichlorohydrin); Cycloaliphatic alcohols such as resorcinol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and 1,1-bis(hydroxymethyl)- from cyclohex-3-ene; It can also be prepared from alcohols with aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. or they are from mononuclear phenols such as resorcinol and hydroquinone, also polynuclear phenols such as bis(4-hydroxyphenyl)methane, 4,4′-dihydroxydiphenyl, bis(4-hydroxyphenyl)sulfone, 1 ,1,2,2-tetrabis(4-hydroxyphenyl)ethane, 2,2,-bis(4-hydroxyphenyl)propane (otherwise known as bisphenol A), 2,2-bis(3, 5-dibromo-4-hydroxyphenyl)propane, and aldehydes such as formaldehyde, acetaldehyde, chloral, and furfuraldehyde with phenols such as phenol itself, and by means of a chlorine atom or each of up to 9 carbon atoms from novolacs formed from phenols substituted in the ring by an alkyl group containing Poly(N-glycidyl) compounds include, for example, epichlorohydrin and amines containing at least two amino-hydrogen atoms such as aniline, n-butylamine, bis(4-aminophenyl)methane, and those obtained by dehydrochlorination of the reaction product of bis(4-methylaminophenyl)methane; triglycidyl isocyanurate; and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea and 1,3-propyleneurea, and hydantoins, such as 5,5-dimethylhydantoin. Epoxide resins having 1,2-epoxide groups attached to different types of heteroatoms, such as N,N,O-triglycidyl derivatives of 4-aminophenol, glycidyl ether-glycidyl esters of salicylic acid, N -Glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycy) Dilhydantoin-3-yl)propane may be used. Epoxides derived from oils are also suitable, such as epoxidized soybean oil, epoxidized castor oil, and the like. Also suitable are epoxides derived or may be derived from per-acid oxidation of unsaturation, such as epoxidized liquid rubbers.

plasticizer

Plasticizers are often used in Part B compositions of two part compositions. Plasticizers may also be used in Part A compositions. A plasticizer may be any liquid or soluble compound that aids in the flexibility of the reactive modules of the composition and/or may act as a carrier vehicle for other components of the composition. Examples are aromatic sulfonamides, aromatic phosphate esters, alkyl phosphate esters, dialkylether aromatic esters, polymeric plasticizers, dialkylether diesters, polyglycol diesters, tricarboxylic acid esters, polyester resins, aromatic diesters, aromatic trees Esters (trimellitate), aliphatic diesters, epoxidized esters, chlorinated hydrocarbons, aromatic oils, alkylether monoesters, naphthenic oils, alkyl monoesters, paraffinic oils, silicone oils, di-n-butyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, 7c9c-phthalate (linear and branched), diisooctyl phthalate, linear 6c,8c,10c phthalate, diisononyl phthalate, linear 8c-10c phthalate, linear 7c-11c phthalate, diisodecyl phthalate, linear 9c-11c phthalate, diundecyl phthalate, diisodecyl glutarate, di-2-ethylhexyl adipate, di -2-ethylhexyl azelate, di-2-ethylhexyl sebacate, di-n-butyl sebacate, diisodecyl adipate, triethylene glycol caprate-caprylate, triethylene glycol 2-ethylhexanote, Dibutoxyethyl adipate, dibutoxyethoxyethyl adipate, dibutoxyethoxyethyl formal, dibutoxyethoxyethyl sebacate, tri-2-ethylhexyl trimellitate, tri-(7c-9c (linear)) trimellitate, tri-(8c-10c (linear)) trimellitate, triethyl phosphate, triisopropyl phenyl phosphate, tributyl phosphate, 2-ethylhexyl diphenyl phosphate, trioctyl phosphate, isodecyl diphenyl phosphate tri Phenyl phosphate, triaryl phosphate synthesis, tributoxyethyl phosphate, tris(-chloroethyl) phosphate, butylphenyl diphenyl phosphate, chlorinated organic phosphate, cresyl diphenyl phosphate, tris(dichloropropyl) phosphate, isopropylphenyl di phenyl phosphate, tricxylenyl phosphate, tricresyl phosphate, or diphenyl octyl phosphate.

block copolymer

When used, the block copolymer can be any block copolymer capable of contributing to the desired physical properties of the disclosed compositions.

Block copolymer rubbers can be constructed using blocks of butadiene or isoprene and styrene (eg SBS, SIS, SEBS and SB), commercial examples of which are KRATON D from Shell Chemical Co. -1116 and other KRATON D-grade elastomers, available from Dexco as VECTOR 2411IP.

Other elastomers having a Tg of less than about 25° C. that are soluble in the methacrylate/acrylate monomers may be used in place of polychloroprene and/or block copolymer rubbers. Examples of these include homopolymers of epichlorohydrin and copolymers thereof with ethylene oxide (available as HYDRIN from Zeon Chemicals), acrylate rubber pellets (available as HYTEMP from Zeon), polyisoprene rubber , polybutadiene rubber, nitrile rubber, and SBR rubber (a random copolymer of butadiene and styrene).

Another block copolymer may also be a styrene maleic anhydride copolymer represented by the formula:

wherein v is 1 to 12; w is 1 to 6; n is 1 to 50.

Styrene maleic anhydride copolymers are well known and some of them are commercially available, for example, under the trade designation SMA EF80 from Sartomer Company, Inc., Exton, PA, USA. It is possible. Styrene maleic anhydride copolymers represent copolymerization products of styrene and maleic anhydride and are characterized by alternating blocks of styrene and maleic anhydride moieties.

Amphiphilic block copolymers may be particularly preferred. Arkema offers amphiphilic block copolymers for sale commercially under the trade designation NANOSTRENGTH. These block copolymers are currently available in two versions: SBM and MAM. SBM copolymers are reported to be made of polystyrene, 1,4-polybutadiene and syndiotactic poly(methyl methacrylate).

Additionally, polymeric materials constructed from polymethyl methacrylate (“PMMA”) and polybutyl acrylate (“PB”) may also be used. Polymeric materials within this class are referred to as polymethylmethacrylate-block-polybutylacrylate-block polymethylmethacrylate copolymers (“MAM”).

As reported by Arkema, MAM consisting of about 70% PMMA and 30% PB is a triblock copolymer. MAMs are constructed from distinct segments, which provide the ability to self-assemble at the molecular scale. That is, M imparts hardness to the polymer, and A imparts elastomeric properties to the polymer.

Rigid polymer segments tend to be soluble in (meth)acrylates, while elastomeric segments provide toughness to polymeric (meth)acrylates, which form upon curing. MAM also enhances mechanical properties without compromising intrinsic physical properties. MAM is currently commercially available under the trade designation NANOSTRENGTH in several different grades (ie, E-21 and M-52N).

Arkema advances its NANOSTRENGTH product line as an acrylic block copolymer that is compatible with many polymers, many of which are major industrial epoxy resins, depending on the manufacturer. See also US Pat. No. 6,894,113, in which the '113 patent in its abstract refers to a thermoset material having improved impact resistance. Impact resistance is defined as S-B-M, B-M and M-B-M blocks, wherein each block has an intermediate linked to the other by a covalent bond or to one of the blocks by a covalent bond and to the other by another covalent bond, and M is PMMA a homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate, wherein B is incompatible with the thermosetting resin and the M block, its glass transition temperature Tg is less than the working temperature of the thermosetting material, and S is the thermosetting resin from 1 to 80% of an impact modifier comprising at least one copolymer that is incompatible with the B block and the M block and its Tg or its melting temperature is greater than the Tg of B).

Another commercially available example of an amphiphilic block copolymer is the polyether block copolymer known under the trade designation FORTEGRA 100 from The Dow Chemical Company. Dow describes FORTEGRA 100 as a low viscosity toughener designed for use as a high efficiency second phase in amine cured epoxy systems. FORTEGRA 100 is reported to provide improved toughness without significantly affecting the viscosity, glass transition temperature, corrosion resistance, cure rate or chemical resistance of the final coating or composition. FORTEGRA 100 is also reported to be useful for compounding into standard bisphenol A and bisphenol F epoxy systems because it does not participate in the epoxy curing reaction. As a second phase toughener, FORTEGRA 100 progresses to be effective when formulated in certain volume fractions of the final film or part, typically 3% to 8% by dry volume is said to achieve a toughening effect.

Additional block copolymers include those comprising both hydrophobic and hydrophilic segments or moieties of the general formula:

-[(R ¹ ) _v -(R ² ) _w ] _n -

wherein R ¹ is independently a hydrophobic olefin such as ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, or 4-methyl-1-pentene or a polymerizable hydrophobic aromatic hydrocarbon such as styrene; each R ² is a hydrophilic acid anhydride, such as maleic anhydride; v is 1 to 12; w is 1 to 6; n is 1 to 50.

The ratio of the hydrophobic segment to the hydrophilic segment in the styrene maleic anhydride block copolymer may be at least 2:1, such as 3:1 to 12:1. The hydrophilic segment in the block copolymer should comprise an anhydride, such as maleic anhydride. The hydrophobic segment in the block copolymer should include at least one of ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, or styrene. Preferably, the block copolymer should be made of a hydrophilic segment comprising maleic anhydride and a hydrophobic segment comprising styrene.

References to the following patent documents indicate amphiphilic block copolymers suitable for use herein and are incorporated herein by reference in their entirety. U.S. Patent No. 7,745,535 discloses that at least one block comprises: a) acrylic acid, methacrylic acid, and salts, esters, anhydrides and amides of acrylic acid and methacrylic acid; dicarboxylic anhydride; carboxyethyl acrylate; and a hydrophilic central block prepared from one or more monomer units selected from acrylamide; and b) an amphipathic multiblock copolymer that is a profiled block consisting of hydrophobic endblocks, wherein the copolymer is water insoluble, water indispersible, and not soluble or dispersible in C _1-3 alcohols. charge

U.S. Patent No. 7,820,760 describes (a) an epoxy resin; (b) at least one epoxy resin miscible block segment and at least one epoxy resin immiscible block segment, wherein the non-miscible block segment comprises at least one polyether structure, provided that the immiscible block The polyether structure of the segment contains amphiphilic block copolymers containing at least one or more alkylene oxide monomer units having at least 4 carbon atoms; and (c) at least one curing agent. The amphiphilic block copolymer in the '760 patent is any polyether block copolymer, such as a PEO-PBO diblock copolymer or a PEO-PBO-PEO triblock copolymer. The amphiphilic block copolymer is present in the '760 patent in an amount such that when the epoxy resin composition is cured, the bond strength of the resulting cured epoxy adhesive resin composition is increased compared to an epoxy resin composition without the amphiphilic polyether block copolymer. exist.

U.S. Patent No. 7,670,649 discloses (a) an epoxy resin; (b) at least one epoxy resin miscible block segment, wherein the non-miscible block segment comprises at least one polyether structure, provided that the polyether structure of the non-miscible block segment comprises at least one or more alkyl an amphiphilic block copolymer containing ren oxide monomer units) and at least one epoxy resin immiscible block segment; and (c) a nitrogen-containing curing agent in an amount sufficient to cure the coating composition at an ambient temperature of less than about 60° C.; When the epoxy resin composition is cured, the toughness of the resulting cured epoxy resin composition increases.

U.S. Patent No. 6,887,574 describes (a) at least one flame retardant epoxy resin; (b) at least one amphiphilic block copolymer; and (c) a curing agent. These components are present in the curable composition in appropriate amounts and proportions such that, upon curing, the block copolymer self-assembles into a nanostructured morphology, such as a worm-like micelle morphology. The resulting cured product is reported to have a greatly increased high rupture resistance; Enables the use of flame retardant epoxies in applications where rupture resistance is an issue.

US Patent Application Publication No. 2008/0287595 discloses (1) a thermosetting resin selected from an epoxy resin, an epoxy vinyl ester resin, an unsaturated polyester resin, or mixtures thereof, and (2) an amphiphilic mimic dispersed in a thermosetting resin ( mock) relates to a composition comprising the copolymer.

International Patent Publication No. WO 2010/008931 relates to structural composites using block copolymer toughening agents to increase the rupture resistance (toughness) of the structural composites. The structural composite comprises (i) a carbon fiber toughening material and (ii) a thermosetting resin composition; wherein the thermosetting resin composition comprises (a) a thermosetting resin and (b) at least one block copolymer toughening agent.

International Patent Publication No. WO 2009/018193, comprising an epoxy resin, a curing agent, an amphiphilic toughening agent, and an inorganic nanofiller, wherein the toughening agent forms a second phase having at least one dimension on the nanometer scale. Curable compositions, cured compositions, and methods of forming the same.

The block copolymer may be used herein in an amount of up to about 50 weight percent, preferably 5 to 40 weight percent, based on the total weight of the adhesive composition.

The glass transition temperature (“Tg”) of the block copolymer should be greater than about 40°C. In one embodiment, the Tg of the block copolymer is from about 40°C to about 155°C.

The Tg of a polymer is the temperature at which the polymer becomes brittle when cooled and soft when heated. More specifically, Tg defines a pseudo-secondary phase transition in which, upon cooling, the polymer acquires a glassy structure with properties similar to those of crystalline materials. Above the Tg, the polymer becomes soft and is capable of plastic deformation without rupture. Although Tg is sometimes described as the "softening temperature" of a polymer, it is not uncommon for a polymer to begin to soften at temperatures below the Tg. This is because, due to the nature of many non-crystalline polymers, softening of the polymer may occur over a range of temperatures rather than abruptly at a single temperature value. Tg generally refers to the midpoint of this range, although polymers may begin to soften at different temperatures. For the purposes of this application, the Tg of a polymer refers to the value determined by ASTM E-1356.

In addition to becoming brittle at temperatures below its Tg, polymers also generally become drier and less tacky than when the same polymer is heated to a temperature above its Tg. The tacky polymer will adhere to the surface more readily upon application of pressure than the non-tacky polymer alone. The importance of incorporating copolymers that have a Tg greater than 40° C. and therefore are dry or only slightly tacky at this point will become more apparent from the discussion below.

other additives

The Part B composition may contain additional additives such as fillers, lubricants, thickeners, and colorants. The filler provides bulk without sacrificing the strength of the adhesive and can be selected from high or low density fillers.

Low-density fillers are of particular importance because the resulting final product would otherwise have a lower density than a filler-free product, but would have the same strength characteristics as without fillers.

Packaging and mixing

Each of the Part A and Part B compositions are packaged in separate containers, such as bottles, cans, tubes, or drums.

The Part A and Part B compositions are mixed in a volume ratio of about 3 to 50 to 1, such as about 5 to 20 to 1. Preferably, the volume ratio is 10:1.

Mixing of the two parts may use a mixing nozzle that has fluid input to the two components, performs a suitable mixing operation, and dispenses the adhesive mixture directly onto the surface to be bonded. An example of a commercially available mixing and dispensing device is sold under the trade name MIXPAC, which is available from Sulzer Mixpac USA (Salem, New Hampshire, USA).

The two parts may also be manually mixed in a container, such as a bowl, bucket, or other container, but the operator must ensure that the mixing is thorough. As an aid to ensuring that the mixing is complete, each part can be blended with a dye or pigment so that the third color is formed after mixing. For example, one part may have a yellow dye and the other part may have a blue dye, so the complete adhesive composition will be green after mixing.

After mixing at room temperature, the composition exhibits an open time of at least about 3 hours, as measured by a Pico Technologies USB TC-08 thermocouple data logger, but at its peak cure temperature (or T _peak ) within less than about 1 hour thereafter. reach

Also provided herein are methods of making a two-part adhesive composition. The method comprises (i) a (meth)acrylate component; and (ii) an amine; (i) providing a second portion comprising a fatty acid peroxide.

Further provided herein are methods of bonding a first surface to a second surface. The method comprises (a) (i) a (meth)acrylate component; and (ii) a first portion comprising an amine; and (b) (i) a second part comprising a fatty acid peroxide; Apply to one, mating the first and second surfaces while having the composition mixed between the two mating surfaces, curing the composition and bonding the first and second surfaces.

In these methods, the first part and the second part are mixed in a ratio of 0.5 to 15 parts Part A composition to 1 part Part B composition by volume.

Example

Example 1 -- Part A composition

In Table 1 Part A, a model Part A composition was prepared from the ingredients listed in the amounts indicated.

Table 1

Part A

In Table 2 Part A, three Part A compositions are shown: Sample No. 1 (control) represents the composition from Table 1 Part A wherein 2 weight percent of p-diethanol amine toluene (p-DEA) was included in the Table 1 Part A composition; sample No. 2 represents the composition from Table 1 Part A with 2 weight percent THQ-CN added to 98 weight percent Table 1 Part A composition; sample No. 3 represents the composition from Table 1 Part A in which 2 weight percent of THQ-NO ₂ was added to 98 weight percent of Table 1 Part A composition.

Table 2

Part A

Example 2 - Part B composition

In Table 1 Part B, a model Part B composition was prepared from the ingredients listed in the amounts indicated.

Table 1

Part B

In Table 2 Part B, three compositions are shown: Sample No. 1 represents the composition from Table 1 Part B wherein 37 weight percent of benzoyl peroxide is added to 63 weight percent of Table 1 Part B composition; sample No. 2 represents the composition from Table 1 Part B wherein 37 weight percent lauroyl peroxide is added to 63 weight percent Table 1 Part B composition; sample No. 3 represents the composition from Table 1 Part B wherein 37 weight percent lauroyl peroxide is added back to the Table 1 Part B composition at 63 weight percent.

Table 2

Part B

Example 3 -- Mixing

Part A and B compositions from Table 2 were mixed together into the mixed composition in a vessel at a volume ratio of 10:1 and mixed with a Pico Technologies USB TC-08 thermocouple data logger so that reactivity measurements over temperature and time could be recorded. placed in the prepared composition. Some of the measurements are captured in Table 3.

The composition was also applied to an anodized aluminum wrap shear coupon and was paired with another anodized aluminum wrap shear coupon with an overlap of 0.5". The coupons were placed in assessment for set time. Set time measurements are also shown in Table 3 is recorded in

Table 3

Another measurement is shown in FIG. 1 . In FIG. 1 , data is accumulated every minute to show the time required for curing initiation (or T _onset ), the time the entire curing profile develops, and the peak exothermic temperature at that time (or T _peak ).

As can be seen, for the control sample (Sample No. 1), the T _onset begins within about 1 to about 2 minutes after mixing and the T _peak appears within about 7 to about 8 minutes after mixing. On the other hand, sample No. 2 requires almost 4 hours (about 202 to 230 minutes) before the onset of T _onset , and the T _peak appears within about 231 to about 233 minutes. Also, sample No. 3 requires more than 3 hours (about 181 to 198 minutes) for T _onset to begin and the T _peak appears within about 199 to about 201 minutes.

Claims (20)

(a) (i) a (meth)acrylate component;
(ii) amines
A first part comprising; and
(b) (i) fatty acid peroxide
a second part comprising
A two-part curable composition comprising a. The composition of claim 1 , wherein when the Part A composition and the Part B composition are mixed together, the composition exhibits an open time of at least about 3 hours, as measured by a PICO Technologies USB TC-08 thermocouple data logger. Thereafter, the composition cures in less than about 60 minutes. The composition of claim 1 , wherein the Part A composition comprises: vinyl terminated polybutadiene in liquid form at room temperature; reactive acid component; 1,4-quinone and at least one of triaryl or alkaryl phenylphosphine. 4. The composition of claim 3, wherein the 1,4-quinone is naphthoquinone, benzoquinone and derivatives thereof. 4. The composition of claim 3, wherein the 1,4-quinone is present in an amount of about 0.05 weight percent or less. 4. The composition of claim 3, wherein the triaryl or alkaryl phenylphosphine is present in an amount of at least about 0.5 weight percent. The composition of claim 1 , wherein the (meth)acrylate component of the Part A composition is methyl (meth)acrylate, (meth)acrylic acid, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth) acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl ( Meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl ( Meth) acrylate, phenyl (meth) acrylate, tolyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-( Meth)acryloyloxypropyl trimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-purple Luoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylic Late, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluoro Rhodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylol propane trimethacrylate, dipentaerythritol monohydroxypentacrylic Late, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butyl Rene glycol diacrylate, trimethylopropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxy penta( Meth) acrylate, tri (propylene glycol) di (meth) acrylate, neopentyl glycol propoxylate di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate , triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and combinations thereof. The composition of claim 1 , wherein the amine is selected from:

wherein R is optional but, if present, may occur 1-4 times, interrupted by one or more heteroatoms and/or C which may be functionalized by halogen, -OH, -COOH, -CN, -NH ₂ or -NO ₂ . _1-5 alkyl; halogen; -OH; -COOH; -CN; -NH ₂ or -NO ₂ ; X is C _1-5 alkyl or C _7-20 alkaryl, one of which may be interrupted by one or more heteroatoms, which are functionalized by at least one electron withdrawing group such as —CN or —NO ₂ , and ; z is 1-3. The method of claim 1,
Amin

A composition selected from 4. The composition of claim 3, wherein the reactive acid component is a sulfonic acid or a sulfonic acid derivative. 4. The composition of claim 3, wherein the reactive acid component is selected from the group consisting of phosphoric acid, phosphoric acid derivatives, and phosphate esters. 4. The composition of claim 3, wherein the reactive acid component is hydroxyl ethyl methacrylate phosphate ester. The composition of claim 1 , wherein the fatty acid peroxide has from about 8 carbon atoms to about 18 carbon atoms. The composition of claim 1 , wherein the fatty acid peroxide is a member selected from lauroyl peroxide, didecanoyl peroxide, dimyristyl peroxydicarbonate and dicetyl peroxydicarbonate. The composition of claim 1 , further comprising an epoxy resin in the Part B composition. 16. The composition of claim 15, wherein the epoxy resin of the Part B composition is a cycloaliphatic epoxide, an epoxy novolak resin, a bisphenol-A epoxy resin, a bisphenol-F epoxy resin, a bisphenol-A epichlorohydrin-based epoxy resin, an alkyl epoxide; A composition selected from the group consisting of limonene dioxide, polyfunctional epoxides, and combinations thereof. 16. The composition of claim 15, wherein the epoxy resin of the Part B composition is a liquid bisphenol A epichlorohydrin epoxy resin. (a) (i) a (meth)acrylate component; and
(ii) amines
providing a first portion comprising; and
(b) (i) fatty acid peroxide
providing a second portion comprising
A method for preparing a two-part adhesive composition comprising: (a) (i) a (meth)acrylate component; and
(ii) amines
a first part comprising; and
(b) (i) fatty acid peroxide
a second part comprising
providing a two-part composition comprising:
mixing the first part and the second part;
applying the mixed composition to at least one of the first surface or the second surface;
mating the first surface and the second surface while having the composition mixed between the two mating surfaces, and
curing the composition and bonding the first surface and the second surface;
A method of bonding a first surface to a second surface comprising: 19. The method of claim 18, wherein the Part A composition and the Part B composition are mixed in a ratio of 0.5 to 15 parts Part A composition to 1 part Part B composition by volume.

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